EP3880647A1 - Iron-catalyzed selective production of methyl esters from aldehydes - Google Patents

Iron-catalyzed selective production of methyl esters from aldehydes

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Publication number
EP3880647A1
EP3880647A1 EP19818316.2A EP19818316A EP3880647A1 EP 3880647 A1 EP3880647 A1 EP 3880647A1 EP 19818316 A EP19818316 A EP 19818316A EP 3880647 A1 EP3880647 A1 EP 3880647A1
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EP
European Patent Office
Prior art keywords
catalyst
iron
methyl esters
aldehydes
methanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19818316.2A
Other languages
German (de)
French (fr)
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EP3880647B1 (en
Inventor
Sumit Chakraborty
Steven J. ADAMS
Robert Thomas Hembre
Leslie Sharon Depew
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Eastman Chemical Co
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Eastman Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring

Definitions

  • the invention generally relates to the field of organic chemistry. It particularly relates to the production of methyl esters from aldehydes using a novel iron-based catalyst.
  • Esters are among the most important and abundant functional groups in chemistry and they are widely found in food, pharmaceutical, flavor, and fine and bulk chemical industries. There are classical methods, e.g.
  • the invention is a process for preparing esters comprising: a) combining an aldehyde having the formula RiCO with an alcohol having the formula R2OH to form a first mixture;
  • the catalyst has the structure (1 ):
  • M2EH refers to methyl-2-ethylhexanoate.
  • TEG triethylene glycol
  • TEG-2EH refers to triethylene glycol 2-ethylhexanoate.
  • 2-HEH refers to 2-ethylhexaldehyde.
  • MeOH refers to methanol
  • homogeneous dehydrogenation catalysts supported by pincer-type ligands, also showed negligible reactivity and selectivity toward forming 2-EHMe.
  • Milstein’s (PNN)Ru(H)(CO)CI catalyst in the presence of KOH afforded 2-EHMe and 2-ethylhexylalcohol (2-EH) with a relative ratio of 1 :1.2 and the overall conversion of 2-HEH reached to 22% after 6 hours at 90° C (entry 4).
  • the homoester of 2-HEH aldehyde, (2-ethylhexyl)2-ethylhexanoate (2EH2EH) was also formed in a considerable amount (1 1 %) during this reaction.
  • Takasago’s Ru-MACHO catalyst afforded 2-EH and 2EH2EH as major products and 2-EHMe was only produced in small quantities (entry 5).
  • the liquid sample was analyzed by GC and GC-MS to determine the yield of methyl 2- ethylhexanoate (97.8 wt%) and identify other side-products Synthesis of methyl benzoate from benzaldehyde.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for making methyl esters in high yields is provided. The process comprises contacting aliphatic or aromatic aldehydes and methanol with an iron catalyst, to catalyze the dehydrogenative coupling between aliphatic or aromatic aldehydes and methanol. The reaction is highly selective (<99.9%) toward the formation of methyl esters over homoesters and alcohols and operates at temperatures of less than 100° C for 2-8 hours.

Description

IRON-CATALYZED SELECTIVE PRODUCTION OF METHYL ESTERS
FROM ALDEHYDES
FIELD OF THE INVENTION
[0001] The invention generally relates to the field of organic chemistry. It particularly relates to the production of methyl esters from aldehydes using a novel iron-based catalyst.
BACKGROUND OF THE INVENTION
[0002] Esters are among the most important and abundant functional groups in chemistry and they are widely found in food, pharmaceutical, flavor, and fine and bulk chemical industries. There are classical methods, e.g.
reaction with carboxylic acid derivatives, carbonylation and the Tischenko reaction, which could be used to prepare ester compounds. The coupling of aldehydes with alcohols and coupling of two alcohols in the presence of external oxidants can also form esters. An alternative approach is the dehydrogenative coupling of two alcohols or aldehydes with alcohols with the release of H2.
[0003] Acceptorless dehydrogenative homo-coupling of alcohols have been reported however a need still exists for a catalytic process that allows for the chemoselective dehydrogenative cross-coupling of aldehydes with methanol to afford corresponding methyl esters in high yields and moderate selectivities.
[0004] The present invention addresses this need as well as others, which will become apparent from the following description and the appended claims.
SUMMARY OF THE INVENTION
[0005] The invention is as set forth in the appended claims.
[0006] In one embodiment the invention is a process for preparing esters comprising: a) combining an aldehyde having the formula RiCO with an alcohol having the formula R2OH to form a first mixture;
b) heating the first mixture in the presence of an iron catalyst to form an ester having the formula RiC0R20and H2; wherein Ri is a C4 to Cs aliphatic, alicyclic or aromatic group and wherein R2 is a Ci to C4 group.
[0007] In another embodiment the catalyst has the structure (1 ):
[0008] It has been surprisingly discovered that an iron catalyst mediates selective formation of methyl-2-ethylhexanoate via a reaction between 2- ethylhexenal (2-EHenal) and MeOH under mild conditions (<100° C). We have also demonstrated that an equimolar mixture of 2-EHMe and 2-EH alcohol is produced when 2-HEH is used as the feedstock
DETAILED DESCRIPTION OF THE INVENTION
[0009] As used herein the following terms have the meaning as described below:
[0010] The term“M2EH” refers to methyl-2-ethylhexanoate.
[0011] The term“TEG” refers to triethylene glycol.
[0012] The term“TEG-2EH” refers to triethylene glycol 2-ethylhexanoate.
[0013] The term“2-HEH” refers to 2-ethylhexaldehyde.
[0014] The term“MeOH” refers to methanol.
[0015] The term“2-EHMe” refers to methyl 2-ethylhexanoate
[0016] The term“2EH” refers to 2-ethylhexyl alcohol.
[0017] The term“2EH2EH” refers to (2-ethylhexyl)2-ethylhexanoate. [0018] As used herein, the indefinite articles“a” and“an” mean one or more, unless the context clearly suggests otherwise. Similarly, the singular form of nouns includes their plural form, and vice versa, unless the context clearly suggests otherwise
[0019] While attempts have been made to be precise, the numerical values and ranges described herein should be considered approximations (even when not qualified by the term“about”). These values and ranges may vary from their stated numbers depending upon the desired properties sought to be obtained by the present invention as well as the variations resulting from the standard deviation found in the measuring techniques. Moreover, the ranges described herein are intended and specifically contemplated to include all sub-ranges and values within the stated ranges. For example, a range of 0 to 100 is intended to describe and include all values within the range including sub-ranges such as 0.1 -99.9, 60 to 90 and 70 to 80.
[0020] We examined a reaction with 2-ethylhexaldehyde (2-HEH) and methanol (MeOH) (Table 1 ). In the absence of a catalyst, reacting 2- ethylhexaldehyde with excess of MeOH (5 equivalents) converted the aldehyde into a dimethyl acetal in MeOH at 90° C. No ester formation was observed under catalyst-free condition. Next, several homogeneous catalysts were screened to facilitate the formation of corresponding methyl ester (methyl 2-ethylhexanoate). These results are summarized in Table 1. Simple metal precursor complexes such as [Cp*RhCl2]2, [Cp*lrCl2]2, Ru3(CO)i2 (Cp* = 1 ,2,3,4,5-pentamethylcyclopentadiene) failed to produce any methyl 2- ethylhexanoate (entries 1 -3) and only trace amounts of 2-ethylhexyl alcohol was produced in these reactions. Ruthenium and iridium-based
homogeneous dehydrogenation catalysts, supported by pincer-type ligands, also showed negligible reactivity and selectivity toward forming 2-EHMe. For example, Milstein’s (PNN)Ru(H)(CO)CI catalyst in the presence of KOH afforded 2-EHMe and 2-ethylhexylalcohol (2-EH) with a relative ratio of 1 :1.2 and the overall conversion of 2-HEH reached to 22% after 6 hours at 90° C (entry 4). The homoester of 2-HEH aldehyde, (2-ethylhexyl)2-ethylhexanoate (2EH2EH), was also formed in a considerable amount (1 1 %) during this reaction. In addition to Milstein’s catalyst, Takasago’s Ru-MACHO catalyst afforded 2-EH and 2EH2EH as major products and 2-EHMe was only produced in small quantities (entry 5).
Table 1. Catalyst Screening Studies for 2EH-MeOH Coupling Reaction.
[0021] This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. EXAMPLES
General Experimental Information
[0022] Unless otherwise noted, all the organometallic compounds were handled under a nitrogen atmosphere using standard Schlenk and glovebox techniques. Anhydrous methanol (99.7% grade), toluene, p-xylene, Aromatic 200 and mesitylene (98%) were purchased from commercial sources and stored with 4A molecular sieves. All aldehydes were purchased from commercial sources and freshly vacuum-distilled prior to use. Other commercially available catalysts were purchased from respective commercial sources and used without further purification. 1H NMR spectra were recorded on Bruker Avance-500 MHz spectrometers. Chemical shift values in 1H NMR spectra were referenced internally to the residual solvent resonances (d 7.16 for benzene-afe). Iron catalyst was prepared using the literature procedure (Scheme 1 ).
Synthesis of Iron Catalyst (1), Scheme 3.
[0023] Under a nitrogen atmosphere, a 500 mL Schlenk flask, fitted with a condensor and stir bar, was charged with iron dodecacarbonyl, tetraphenyl cyclopentadienone, and 200 mL anhydrous toluene. The resulting mixture was heated to 80° C for 20 hours, cooled to room temperature, and mixture was passed through silica gel column to elute the desired catalyst as orange- yellow liquid. Evaporation of the solvent afforded the product in 86% isolated yield.
Synthesis of methyl 2-ethylhexanoate from 2-ethylhexaldehyde.
[0024] Under a nitrogen atmosphere, an oven-dried 25 ml_ Schlenk tube equipped with a magnetic stir-bar and a Teflon plug was charged with the iron catalyst (1 mol%), 2-ethylhexaldehyde (2-HEH) (1.6 ml_, 10 mmol), and anhydrous methanol (2 ml_). The resulting mixture was heated at 90° C for 3 hours using an oil-bath. After that the vessel was gradually allowed to come to room temperature and the volatiles (H2, MeOH vapor) were carefully removed by opening the Teflon plug inside a hood. The liquid sample was analyzed by GC and GC-MS to determine the yield of methyl 2- ethylhexanoate and identify side-products.
Synthesis of methyl 2-ethylhexanoate from 2-EHenal.
[0025] Under a nitrogen atmosphere, an oven-dried 100 ml_ Schlenk tube equipped with a magnetic stir-bar and a Teflon plug was charged with the iron catalyst (1 mol%), 2-ethyl-2-hexenal (2EHenal) (1.57 ml_, 10 mmol), and anhydrous methanol (2 ml_). The resulting mixture was heated at 90° C for 3 hours using an oil-bath. After that the vessel was gradually allowed to come to room temperature and the volatiles (H2, MeOH vapor) were carefully removed by opening the Teflon plug inside the hood. The liquid sample was analyzed by GC and GC-MS to determine the yield of methyl 2- ethylhexanoate (97.8 wt%) and identify other side-products Synthesis of methyl benzoate from benzaldehyde.
[0026] Under a nitrogen atmosphere, an oven-dried 100 ml_ Schlenk tube equipped with a magnetic stir-bar and a Teflon plug was charged with the iron catalyst (1.0 mol%), benzalaldehyde (1.35 g, 10 mmol, 99% purity), and anhydrous methanol (2 ml_). The resulting mixture was heated at 90° C for 3 hours using an oil-bath. After that the vessel was gradually allowed to come to room temperature and the volatiles (H2, MeOH vapor) were carefully removed by opening the Teflon plug inside the hood. The liquid sample was analyzed by GC and GC-MS to determine the yield of methyl benzoate and identify other side products
[0027] In summary, we have demonstrated that Shvo’s catalyst catalyzes the dehydrogenative coupling between aliphatic or aromatic aldehydes and MeOH to afford corresponding methyl esters in high yields. The reaction is highly selective (up to <99.9%) toward the formation of methyl esters and operates under mild conditions (<100° C, 2-8 hours). The catalytic activity and the structure of the catalyst remain unchanged after several catalytic runs. An iron catalyst (1) shown below exhibited excellent reactivity and selectivity toward the formation of methyl esters from corresponding aldehydes via coupling with MeOH. When one equivalent of 2-EH was treated with five equivalents of MeOH at 90° C in the presence of 1 mol% of (p4-CpMe4)Fe(CO)3 catalyst (1), a mixture containing 50:45 ratio of 2-EHMe and 2-EH were formed after 3 hours (Table 2, entry 1 ). No starting aldehyde remained after the reaction suggesting 100% aldehyde conversion. Traces of 2EH2EH, and unsaturated 2-EH methyl ester were also produced as byproducts in this reaction. The catalytic reaction could also be carried out in non-polar aromatic solvents such as toluene, p-xylene, mesitylene and Aromatic 200 without affecting the reactivity and selectivity. Table 2. Iron-Catalyzed Synthesis of Methyl Esters from Aldehydes.9
aCatalytic Conditions: [catalyst] = 0.025 (M), [aldehyde] = 2.5 (M), MeOH = 25 mmol, 1 ml_, neat conditions, stir speed = 350 rpm, 90 °C (oil-bath temperature). [0028] We have demonstrated that the iron catalyst (1 ) catalyzes
dehydrogenative coupling between aliphatic or aromatic aldehydes and MeOH to afford corresponding methyl esters in moderate to high yields. The reaction is chemoselective toward the formation of methyl esters when substrate containing internal C=C bond is employed and the reaction operates under mild conditions (<100° C, 2-8 hours). Experiments show that the catalytic activity and the structure of the catalyst (1 ) remain unchanged after two catalytic runs.
1 mol%
[0029] Remarkably, the coupling reaction between 2-EHenal and MeOH produced the saturated methyl 2-ethylhexanoate in 89.2% yield (Table 2, entry 2). The rest of the material accounts for unreacted 2EHenal, 2EH2EH, unsaturated esters, and 2-EH. This result indicates that the H2 gas produced during the first 2EHenal-methanol coupling step is utilized to hydrogenate the C=C double bonds in the presence of the iron catalyst. This direct coupling of 2EHenal with methanol is an important discovery because it eliminates the reaction step for producing 2-HEH from 2-EHenal by hydrogenation with a heterogeneous catalyst (Scheme 1 ). In addition to aliphatic substrates, aromatic aldehydes such as benzaldehyde also afforded corresponding methyl esters in ~ 56% yield. This reaction could be used for dimethyl terephthalate (DMT) synthesis using terepthaldehyde as the reagent.
[0030] In the specification, there have been disclosed certain embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being set forth in the following claims.

Claims

CLAIMS We claim:
1. A process for preparing esters comprising:
a) combining an aldehyde having the formula R1CO with an alcohol having the formula R2OH to form a first mixture; b) heating the first mixture in the presence of an iron catalyst to form an ester having the formula RiC0R20and H2;
wherein Ri is a C4 to Cs aliphatic, alicyclic or aromatic group and wherein R2 is a Ci to C4 group.
2. The process of claim 1 wherein R2 is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol and ethylene glycol.
3. The process of claim 1 wherein R2 is methanol.
4. The process of claim 1 wherein step b. is conducted at a temperature of less than 100o C for about 2 hours to about 8 hours.
5. The process of claim 1 wherein the molar ratio of R1CO to R2OH in said first mixture is from 1 :1 to 1 :5.
6. The process of claim 1 wherein the molar amount of catalyst in said first mixture is from about 0.25 mole percent to about 1 mole percent.
7. The process of claim 1 wherein said iron catalyst is represented by the structure:
8. An iron catalyst having the structure:
EP19818316.2A 2018-11-13 2019-11-12 Iron-catalyzed selective production of methyl esters from aldehydes Active EP3880647B1 (en)

Applications Claiming Priority (2)

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US16/188,976 US10590062B1 (en) 2018-11-13 2018-11-13 Iron-catalyzed selective production of methyl esters from aldehydes
PCT/US2019/060818 WO2020102126A1 (en) 2018-11-13 2019-11-12 Iron-catalyzed selective production of methyl esters from aldehydes

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EP3880647B1 EP3880647B1 (en) 2024-09-18

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CN113166028B (en) 2018-11-13 2024-03-12 伊士曼化工公司 Synthesis of esters using heterogeneous AU/TIO2 catalysts
CN119798058B (en) * 2024-12-26 2026-03-20 浙江工业大学 A method for preparing α-alkyl ketone derivatives

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JPS5750942A (en) * 1980-09-12 1982-03-25 Japan Synthetic Rubber Co Ltd Preparation of carboxylic ester
JPS5750941A (en) * 1980-09-12 1982-03-25 Japan Synthetic Rubber Co Ltd Preparation of carboxylic ester
JPH0899933A (en) 1994-09-29 1996-04-16 Mitsubishi Chem Corp Method for producing methacrylic acid ester
JPH09216850A (en) * 1996-02-09 1997-08-19 Mitsubishi Rayon Co Ltd Method for producing carboxylic acid ester
JPH1143463A (en) * 1997-07-30 1999-02-16 Mitsubishi Rayon Co Ltd Method for producing carboxylic acid ester
US6120699A (en) * 1998-09-21 2000-09-19 Basf Corporation Storage stable methylene bis(phenylisocyanate) compositions
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JP2001220367A (en) 2000-02-09 2001-08-14 Asahi Kasei Corp Method for producing carboxylic acid ester and catalyst for production
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US9597673B2 (en) * 2012-05-25 2017-03-21 The Governing Council Of The University Of Toronto Iron catalysts with unsymmetrical PNN'P ligands
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US20150274621A1 (en) * 2014-03-31 2015-10-01 The Procter & Gamble Company Homogeneous Hydrogenation of Esters Employing a Complex of Iron as Catalyst
US9493395B2 (en) 2015-04-07 2016-11-15 Eastman Chemical Company Production of two esters using homogeneous catalyst

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EP3880647B1 (en) 2024-09-18
WO2020102126A1 (en) 2020-05-22
US10590062B1 (en) 2020-03-17
CN113015715B (en) 2024-07-19

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